Ammonium hydrazoate

Ammonium hydrazoate, NH4N3.—The hydrazoate is formed by the interaction of ammonia and a dry, ethereal solution of hydrazoic acid.1 It melts and decomposes violently at 160° C. 

Hydrazoic Acid.—The third compound, which is the other one containing only nitrogen and hydrogen, is not an ammonia derivative. It is known as hydrazoic acid or tri-azoic acid. Its formula is N3H. It is a mono-basic acid while ammonia, NH3, is a base. It forms a salt with ammonia, NH4N3, ammonium hydrazoate. Hydrazoic acid was also discovered by Curtius in 1890. 

Hydrazoic acid behaves as both an oxidising and reducing agent in solution. Thus it will oxidise hydrochloric acid to chlorine, the main products being nitrogen and ammonium ions ... 

Reductions with zinc are carried out in aqueous [160 as well as anhydrous solvents [163 and at different pHs of the medium. The choice of the reaction conditions is very important since entirely different results may be obtained under different conditions. While reduction of aromatic nitro groups in alkali hydroxides or aqueous ammonia gives hydrazo compounds, reduction in aqueous ammonium chloride gives hydroxylamines, and reduction in acidic medium amines (p. 73). Of organic solvents the most efficient seem to be dimethyl formamide [164 and acetic anhydride [755]. However, alcohols have... 

A number of investigations have been devoted to the thermal decomposition of hydrazoic acid or to decomposition produced by electric discharge. Thus Rice and Freamo [50] established that its thermal decomposition at 77°K leads to the formation of a blue-coloured sediment. At a higher temperature, 148°K, it changes colour, forming a white substance which has been identified as ammonium azide. They suggested that the blue colour is caused by the presence of the free imino radical NH. 

The salts of hydrazoic acid, the azides, have solubilities similar to those of the corresponding chlorides. Sodium azide dissolves in water. Silver azide does not dissolve in water or in nitric acid, but dissolves easily in an aqueous solution of ammonia. Lead azide, like lead chloride, is sparingly soluble in cold water but more soluble in hot water it is also soluble in ammonium acetate. 

Bis (Hydroxylamino) Azide (called Dihydroxyl-Ammonium Trinitride by Dennis Isham), (NHaOH)a-HNs, mw 109.10, N64.20% col, trans, leaf-like crysts, nip 66° v sol in w, sol in ale and insol in eth. This compd was prepd in 1906 by Dennis Isham (Ref 1) upon evapg a mixt of hydroxyl amine and hydra-zoic acid, both in methyl ale solns. The recovered crysts were purified by dissolving in a mixt of 1 g methyl ale and 20 p ether, filtering and rapidly evapg the solvent in a vacuum desiccator (See also Ref 2). No expl props were determined (Also see Hydrazoic Acid)... 

The yield from this reaction is greatest if the medium is alkaline, for nitrous acid attacks hydrazoic acid oxidizing it with the liberation of nitrogen. If hydrazine sulfate37 is used in the mixture, the resulting hydrazoic acid is not available for the preparation of lead azide until it has been distilled out of the solution. (Lead ions added to the solution would cause the precipitation of lead sulfate.) The reaction mixture may be acidified with sulfuric acid, a little ammonium sulfate may be added in order that the... 

D. I. Mendeleeff argued that just as primary ammonium mesonitrate, (NH40)(H0)2N0,.is supposed to furnish nitrous oxide by the loss of three mols. of water, so may secondary ammonium mesonitrate, (NHiO)2(HO)NO, furnish hydrazoic acid by the loss of four mols. of water. This would make hydrazoic acid the nitrile of mesonitric acid ... 

T. Curtius and J. Rissom showed that the evaporation of a soln. of manganese carbonate in hydrazoic acid gives a pulverulent, non-crystalline manganese hydroxyazide, Mn(OH)(N3)2, which cannot be purified by re-crystallization. The product is sparingly soluble in water it does not explode by percussion, but does so on a hot plate. L. Wohler and F. Martin gave 203° for the explosion temp, of manganese azide. T. Curtius and J. Rissom obtained a colourless soln. of ferrous azide by the action of sodium azide on a soln. of ferrous ammonium sulphate when boiled, the salt decomposes and when shaken in air, a blood-red soln. of ferric azide is formed. The same salt can also be obtained directly from ferric salts. When the soln. of ferric azide is boiled, ferric hydroxide is precipitated and, added T. Curtius and A. Darapsky, if allowed to stand in... 

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